Car body coating process

ABSTRACT

This invention provides a car body coating process wherein the metal-exposed portion of a shell body, a part or whole of which has been made of plastics-covered metal plates, is electrocoated with use of an electrodeposition paint which contains no coloring pigment and has a bath solid content of at most 10% by weight and which is capable of forming a clear coating film.

[0001] The present invention relates to a car body coating processwherein the metal-exposed portion of shell body of a car body, a part orwhole of which has been made of plastics-covered metal plates, iselectrocoated with use of an electrodeposition paint which contains nocoloring pigment and has a bath solid content of at most 10% by weightand which is capable of forming a clear coating film.

[0002] In the body of passenger car or of small passenger car, theportion which is mainly constituted of sheet metal and which is free ofriggings such as engine or wheels is called shell body. Shell body isusually constituted of a main body, which consists of underbody, sidemember, roof, cowl, upper back, lower back, etc., and outer cover partssuch as hood, front balance, front fender, cowl louver, door, luggage(back door), etc.

[0003] Up to the present, metal plates which have been cut and molded inthe size and shape of each component part have been assembled to formmain body and outer cover parts, which in turn are combined to make ashell body, which is dipped into a cationic electrodeposition paint bathso that the surface, backside, edge surface portion, etc., of the metalplates may be electrocoated, and, thus, the shell body is coated with aprimer film.

[0004] Usually, after conducting this electrodeposition, water-washingis carried out several times with use of ultrafiltration filtrate,deionized water, tap water, etc., so as to remove superfluouselectropaint which has adhered to the electrocoated surface orelectropaint which has collected in the interior of bag-like portion.Then, heating is conducted so that thus formed coating film may becured. Outside portions of shell body are coated with intermediate paintand topcoat paint.

[0005] In car body coating, however, cutting down of effluent from theprocess of water-washing of electrocoating film has recently beenstrongly desired for the sake of step saving, energy saving and CO₂reduction in the coating line, and for the preservation of environment.Moreover, there has further been desired improvement not only inthrowing power of electrodeposition paint to edge surface portion, butalso in chipping resistance, corrosion resistance, etc., of totalcoating film including intermediate coating and top coating.

[0006] In the coating of a car body, on the other hand, there isproposed an inverse method (for example, Japanese Pre-grant PatentPublication No. 41317/1980), in which a substrate is powder-coated andthe resulting coating film is cured, and, thereafter, the uncoatedportion is electrocoated, for the purpose of the reduction of organicsolvent discharged and the improvement of edge surface coatability ofelectrodeposition paint. This method has, however, such problems thatpowder coating facilities need to be newly provided, and that thecorrosion resistance of the boundary portion between powder coating filmand electrodeposition coating film is not sufficient.

[0007] The chief objective of the present invention is to provide a carbody coating method which satisfies the above-mentioned requirements incar body coating and which is free of the above-mentioned defects.

[0008] [Means to Attain the Objective]

[0009] As a result of assiduous study, the inventors of this inventionhave found that the above-mentioned objective can be attained by makinga part or whole of shell body by using previously prepared metal platescovered with plastics layer, and then electrocoating the metal exposedportion of thus made shell body with an electrodeposition paint whichcontains no coloring pigment and has a bath solid content of at most 10%by weight and which is capable of forming a clear coating film, and,thus, have completed this invention.

[0010] Thus, according to the present invention, there is provided a carbody coating process (hereinafter referred to as Process I) which ischaracterized in that main outer parts of a car body is made ofplastics-covered metal plates to form a shell body, and that the metalexposed portion of the shell body is electrocoated with anelectrodeposition paint which contains no coloring pigment and has abath solid content of at most 10% by weight and which is capable offorming a clear coating film.

[0011] According to the present invention, there is also provided a carbody coating process (hereinafter referred to as Process II) which ischaracterized in that car parts which have been made by cutting, moldingand joining plastics-covered metal plates are attached to the main outerportions of main body of a car body which has previously been assembled,and that that the metal exposed portion of thus formed shell body iselectrocoated with an electrodeposition paint which contains no coloringpigment and has a bath solid content of at most 10% by weight and whichis capable of forming a clear coating film.

[0012] The car body coating processes of the present invention aredescribed in more detail in the following.

[0013] The processes of the present invention can be applied mainly tonormal and small passenger car, but can also be applied to truck, bus,motorcycle, and specially equipped vehicles in the same manner.

[0014] As a metal plate to be covered with plastics, metals which haveheretofore been used for car body can be similarly used. As the materialof metal, there may be mentioned, for example, iron, steel, stainlesssteel, aluminium, copper, and alloys containing these metals, and,furthermore, plate of these metals whose surface is plated with zinc,zinc/nickel, iron, etc. For use, they can be processed into coils or cutplates. The thickness of these metal plates is suitably in the range of0.3 to 2.0 mm, particularly 0.5 to 1.0 mm. The surface of these metalplates is preferably subjected to suitable treatment such as grindingtreatment, degreasing treatment or phosphate treatment with a view toimprovement in adhesivity with plastics layer, corrosion resistance,etc.

[0015] As plastic materials to cover the above-mentioned metal plates,there can be used known thermoplastic resins, for example, polyolefinresin such as polyethylene and polypropylene; polyester resin such aspolyethylene terephthalate (PET); polycarbonate resin; epoxy resin;vinyl acetate resin; vinyl chloride resin; fluorine-containing resin;polyvinyl acetal resin; polyvinyl alcohol resin; polyamide resin;polystyrene resin; acrylic resin; polyurethane resin; phenolic resin;polyether resin; cellulose type resin; etc. These plastic materials maycontain color pigment, extender pigment, etc.

[0016] Covering of a metal plate with these plastics materials can beperformed by known methods, which include sticking, onto metal plate,film- or sheet-like plastics formed by such a method as extrusionmolding, injection molding, calender molding or compression molding;sticking with pressure, onto metal plate, molten plastics extruded intofilm or sheet; adhering plastics in powder form onto metal plate bymethods such as fluidized immersion, electrostatic coating, etc. andthen melting by heating. Particularly preferable is the process ofsticking plastics in film or sheet form onto metal plate. Covering of ametal plate with plastics is performed at least on the surface of ametal plate located at outer side of a car body. However, it is possibleto cover both surfaces, if desired. The thickness of the plastics layercovering a metal plate is preferably in the range of usually 1 to 100μm, particularly 3 to 75 μm, more desirably 5 to 50 μm. Moreover, it ispossible to treat the surface of these plastics by corona discharge,plasma, flame, etc., before or after the covering onto the metal plate.

[0017] When a metal plate is to be covered with plastics by means ofsticking film-like or sheet-like plastics onto the metal plate, it ispreferable to previously apply an adhesive to the metal plate and/or toplastics film or sheet in order to increase adhesivity between the two.As such an adhesive there may be mentioned thermosetting orthermoplastic adhesives containing one or more kinds of resins selectedfrom, for example, bisphenol type epoxy resin, resol type epoxy resin,acrylic resin, aminoplast resin, polyester resin, polysiloxane resin,etc., and optionally further containing a curing agent. Further, therecan preferably be used as adhesive triazinethiol type compounds such as2,4,6-trimercapto-S-triazine, 2-dibutylamino-4,6-dimercapto-S-triazine,2,4,6-trimercapto-S-triazine-monosodium salt,2,4,6-trimercapto-S-triazine-trisodium salt, etc.

[0018] In the Process I according to the present invention,plastics-covered metal plates which are prepared by the above-mentionedmanner are cut, molded or jointed to assemble a shell body with.Specifically, from the plastics-covered metal plates, there are producedmain body and outer cover parts, which are then assembled to form ashell body.

[0019] Shell body is such a portion in a car body as is constitutedmainly of sheet metal and is free from riggings such as engine orwheels. Its main body is constituted mainly with parts such asunderbody, side member, roof, cowl, upper back, lower back etc. and theouter cover parts consists mainly of parts such as hood, front balance,front fender, cowl louver, door, luggage (back door), etc. Parts ofouter cover parts are called car parts.

[0020] Underbody here means the floor portion of the cabin, trunk room,etc., and is a generic term for front underbody, front floor, rearfloor, etc. Side member forms the side of a cabin joining with a frontbody, roof panel, underbody, etc., and prevents the car from bendingand/or twisting. Cowl is a panel combining left, right, front and rearpillars. Upper back is a panel combining left and right quarter panels(rear fender) at the back portion of a car body and forming outersurface of the car body.

[0021] In the Process I of the present invention, in order to form theabove-mentioned parts constituting a shell body, a plastics-coveredmetal plate, which has been prepared as mentioned above, is cut to thesuitable shape and size, pressed and molded by a press etc., and, ifnecessary, joined by adhering with adhesive, welding, bolted etc. toprepare parts of the main body such as underbody, side member, roof,cowl, upper back, lower back, etc.; and parts (car parts) of outer coverparts such as hood, front balance, front fender, cowl louver, door,luggage, etc. These cutting, molding and joining can be performed byknown methods. Then the parts of the main body thus formed by using aplastics-covered metal plate are assembled, and joined to form a mainbody, to which parts of outer cover parts (car parts) such as hood,front balance, front fender, cowl louver, door, luggage, etc. areattached.

[0022] While at least the outer surface of the shell body which has thusbeen assembled with using plastics-covered metal plates is covered witha plastics layer, at least the edge surface portion of cutplastics-covered metal plates has its metal portion exposed. Moreover,the back side is preferably covered with plastics layer although metalportion may be exposed. In the Process I of the present invention, theseexposed metal portions are subsequently coated by electrodeposition.

[0023] In Process II according to the present invention, on the otherhand, parts of outer cover parts (car parts) such as hood, frontbalance, front fender, cowl louver, door, luggage, etc. are made bycutting, molding and joining plastics-covered metal plates which havebeen prepared in the above-mentioned manner, and, then, these car partsare attached to the previously assembled main body of a car body, and,thus, a shell body is formed. Each part outer cover parts (car parts)which are made of plastics-covered metal plates may have the samestructure as in the above-mentioned Process I.

[0024] In Process II of the present invention, most or the whole of thecar parts, which constitute outer cover parts, are prepared by using theabove-mentioned plastics-covered metal plate. For example, in order toform each part constituting outer cover parts such as hood, frontbalance, front fender, cowl louver, door, luggage (back door), etc., aplastics-covered metal plate is cut to the suitable shape and size,pressed and molded by a press etc., and, if necessary, joined byadhering with adhesive, welding, bolting etc. to prepare parts (carparts) such as hood, front balance, etc. These cutting, molding andjoining can be performed by known methods. At least the outer surface ofthus formed outer cover parts (car parts) is covered with a plasticslayer, while the edge surface portion of a cut steel plate has anexposed metal portion. The back side may be uncovered and have exposedmetal, or may be covered with plastics.

[0025] In Process II of the present invention, the main body constitutedby underbody, side member, roof, cowl, upper back, lower back, etc., towhich these car parts are attached, are prepared usually without using aplastics-covered metal plate. Instead, an uncovered metal plate is cut,molded and processed, and joined by known methods to form main body. Ashell body is formed by attaching outer cover parts (car parts) whichhas been prepared from plastics-covered metal plate to a main body whichhas been prepared from such an uncovered metal plate. In Process II ofthe present invention, the whole surface of the main body and theexposed metal portion of outer cover parts (car parts) in thus assembledshell body are coated by electrodeposition.

[0026] In Processes I and II of the present invention, metal exposedportions of the assembled shell body is electrocoated with anelectrodeposition paint which contains no coloring pigment, has a bathsolid content of at most 10% by weight and which is capable of forming aclear coating film. The use of such a specific electrodeposition paintmakes it possible to cut down effluent from water-washing process bywhich to remove superfluous electropaint which has adhered toelectrocoated surface.

[0027] In detail, the use of electropaint which contains no coloringpigment and is capable of forming a clear coating film produces thefollowing effects:

[0028] 1) Thermal fluidity of coating film improves with the result thatit becomes possible to form a coating film which is excellent insmoothness and corrosion resistance even though thin. Based on thismerit, it becomes possible to shorten the current application time.

[0029] 2) Although electropaint which has permeated into joint portionsof coated article spouts out in baking process and adheres to otherportions, it causes no popping owing to good thermal fluidity, and,thus, it is possible to simplify a process of water-washing permeatedportions.

[0030] 3) Even though electrodeposition paint adheres to plastic-coveredsurfaces, there occur no uneven drying nor secondary sag since formedcoating film is clear, and, thus, appearance is not damaged.

[0031] 4) In electrocoating bath, pigment or the like does not depositat horizontal portions of article to be coated, and, thus, water-washingprocess can be simplified.

[0032] When there is used an electrodeposition paint which has a bathsolid content of at most 10% by weight, uneven drying hardly occurs eventhough unelectrodeposited material remains on the coated surface afterwater washing, and, thus, decrease of appearance can be inhibited.Moreover, although electropaint which has permeated into joint portionsspouts out during baking, it hardly causes sag or popping.

[0033] In order to remove unelectrodeposited material which has adheredelectrocoated surfaces, there have usually been employed, incombination, primary water-washing with use of a filtrate which has beenprepared by UF (ultrafiltration) of a part of electropaint inelectrobath, and secondary water-washing with use of pure water. Inparticular, water after secondary water-washing is usually dischargedoutside after suitable waste disposal treatment. The amount of thiswaste water is said to be 5 to 10 tons per hour. Owing to theabove-mentioned effects produced by Processes I and II of thisinvention, it becomes possible to omit said secondary water-washing,which shortens water-washing process, and is preferable both in view ofenvironment preservation and economy.

[0034] Incidentally, when the solid content of electrodeposition paintat the time of application exceeds 10% by weight, both the paint whichhas penetrated into, and collected at, joint portions in mold-processedplastics-covered metal plates and the non-electrodeposited paint whichhas adhered both to the surface of plastics-covered metal plates and tothe surface of electrodeposition coating which has deposited on themetal-exposed portion come to have such a high concentration of solidcontents that the above-mentioned primary water-washing becomesinsufficient to fully remove said non-electrodeposited paint, with theresult that the appearance is undesirably damaged.

[0035] There is no particular restriction on the electrodepositionpaints to be used in Processes I and II of the present invention, andboth anionic and cationic type ones will do so long as theelectrodeposition paints satisfy the condition that they contain nocoloring pigment and desirably no extender pigment, and that they have abath solid content of at most 10% by weight, preferably 2 to 7% byweight, further desirably 3 to 5% by weight, and, moreover, that theelectrodeposition paints are capable of forming a clear coating film.Especially preferable is a cationic type electrodeposition paint whichis capable of forming a coating film with excellent corrosionresistance.

[0036] As a cationic electrodeposition paint, there can be mentioned anelectrodeposition paint which is prepared by mixing and dispersing, inaqueous medium, a base resin (a) having hydroxyl group(s) andcationizable group(s), and a blocked polyisocyanate compound (b), and,as circumstances might demand, gelatinizing polymer particles as well.

[0037] As a base resin (a) having hydroxyl group(s) and cationizablegroup(s), the following can be mentioned.

[0038] 1) reaction product of epoxy resin and cationizing agent; 2)acid-protonized product of polycondensate of polycarboxylic acid andpolyamine (cf. U.S. Pat. No. 2,450,940 Specification); 3)acid-protonized product of polyadduct of polyisocyanate compound, polyoland mono- or polyamine; 4) acid-protonized product of copolymer of acryltype or vinyl type monomers having hydroxyl group and amino group [cf.Japanese Laid-Open Patent Publications No. 12395/ 1970 (=U.S. Pat. No.3,455,806) and No. 12396/1970) (=U.S. Pat. No. 3,454,482)]; 5)acid-protonized product polyadduct of polycarboxylic acid resin andalkyleneimine (cf. U.S. Pat. No. 3,403,088 Specification).

[0039] Preferable among the above is a resin included in reactionproducts of the above 1) which is obtained by further making acationizing agent react with epoxy resin which has been prepared byreaction between polyphenol compound and epichlorohydrin, since saidresin forms a coating film which is excellent in corrosion resistance.

[0040] Particularly suitable one among the above-mentioned epoxy resinshas at least two epoxy groups in the molecule, a number averagemolecular weight of at least 200, preferably 800 to 2000, and an epoxyequivalent in the range of 190 to 2000, preferably 400 to 1000. Suchepoxy resins include polyglycidyl ether of polyphenol compound. As saidpolyphenol compound there can be mentioned, for example,bis(4-hydroxyphenyl)-2,2-propane, 4,4′-dihydroxybenzo-phenone,bis(4-hydroxyphenyl)-1,1-ethane, bis(4-hydroxyphenyl)-1,1-isobutane,bis(4-hydroxy-tert-butylphenyl)-2,2-propane, bis(2-hydroxybutyl)methane,1,5-dihydroxynaphthalene, bis(2,4-dihydroxyphenyl)methane,tetra(4-hydroxyphenyl)-1,1,2,2-ethane, 4,4′-dihydroxydiphenyl ether,4,4′-dihydroxydiphenyl sulfone, phenol novolac, cresol novolac, etc.

[0041] These epoxy resins may be further modified by subjecting toreaction with polyol, polyehter polyol, polyester polyol,polyamidoamine, polycarboxylic acid, polyisocyanate compound, etc., andfurther may be graft-polymerized by ε-caprolactone, acrylic monomer,etc.

[0042] Cationizing agent in the above-mentioned 1) is made to react withmost or whole of the epoxy groups existing in the epoxy resin, by whichto introduce cationizable group such as secondary amino group, tertiaryamino group, quaternary ammonium base, etc. into the resin, and, thus,there is given a base resin (a) having a hydroxyl group(s) and acationazable group(s) by reacting.

[0043] As such a cationazing agent, there can be mentioned aminecompound, for example, primary amine, secondary amine, tertiary amine,polyamine, etc. Here, there can be mentioned as a primary aminecompound, for example, methylamine, ethylamine, n-pro-pylamine,isopropylamine, monoethanolamine, n-propanolamine, isopropanolamine,etc.; as a secondary amine compound, for example, diethylamine,diethanolamine, di-n-propanolamine, diisopropanolamine,N-methylethanolamine, N-ethylethanolamine, etc.; and as a tertiary aminecompound, for example, triethylamine, triethanolamine,N,N-dimethylethanolamine, N-methyldiethanolamine,N,N-di-ethylethanolamine, N-ethyldiethanolamine, etc. As a polyaminethere can be mentioned, for example, ethylenediamine,diethylenetriamine, hydroxyethylaminoethylamine, ethylaminoethylamine,methylaminopropylamine, dimethylaminoethylamine,dimethylaminopropylamine, etc.

[0044] As a hydroxyl group in the base resin (a), there may be mentioneda primary hydroxyl group which is introduced by, for example, a reactionwith an alkanol amine in the above-mentioned cationizing agent, or by aring-opening reaction with caprolactone which may be introduced in theepoxy resin, or by a reaction with a polyol, etc.; a secondary hydroxylgroup in the epoxy resin etc. Among these, a primary hydroxyl groupintroduced by a reaction with an alkanolamine is preferable due to itsexcellent crosslinking reactivity with a blocked polyisocyanate compound(crosslinking agent). The amount of hydroxyl groups in the base resin(a) is preferably in the range of generally 20 to 5000 mgKOH/g,particularly 100 to 1000 mgKOH/g. Particularly, it is preferable thatthe primary hydroxyl group equivalent be in the range of 200 to 1000mgKOH/g. The amount of a cationizable group is preferably at least theminimum limit which is necessary for the dispersion of the base resin(a) in water, preferably in the range of 3 to 200, particularly 5 to150, and especially 10 to 80, calculated as KOH (mg/g solid content)(amine value).

[0045] It is desirable that the base resin (a) does not substantiallycontain a free epoxy group.

[0046] Blocked polyisocyanate compound (b) as a crosslinking agent is acompound in which substantially all isocyanate groups in thepolyisocyanate compound are blocked by a volatile blocking agent. Whenheated over the predetermined temperature (usually 100 to 200° C.), theblocking agent is dissociated to regenerate an isocyanate group whichtakes part in the crosslinking reaction with hydroxyl group of the baseresin (a).

[0047] Polyisocyanate compound is a compound having at least twoisocyanate groups in the molecule, examples of which include aliphaticdiisocyanate such as hexamethylene diisocyanate, trimethylenediisocyanate, tetramethylene diisocyanate, dimer acid diisocyanate,lysine diisocyanate, etc.; alicyclic diisocyanate such as isophoronediisocyanate, methylenebis(cyclohexylisocyanate), methylcyclohexanediisocyanate, cyclohexane diisocyanate, cyclopentane diisocyanate, etc.;aromatic diisocyanate such as xylylene diisocyanate, tolylenediisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate,toluidine diisocyanate, etc.; urethanation adducts, biuret type adducts,isocyanuric ring type adducts of these polyisocyanate compounds, etc.

[0048] As a blocking agent to block a free isocyanate group of thesepolyisocyanate compounds, there can be used known blocking agents ofphenol type, alcohol type, active methylene type, mercaptan type, acidamide type, imide type, amine type, imidazole type, urea type, carbamicacid type, imine type, oxime type, sulfurous acid type, lactam type,etc.

[0049] As for the constitutional proportion of the base resin (a) andthe blocked polyisocyanate compound (b), the former preferably accountsfor 40 to 90%, particularly 50 to 80%, and the latter accounts for 60 to10%, particularly 50 to 20%, each based upon the total solid contentweight of both components (a) and (b).

[0050] A cationic electrodeposition paint which is usable in Processes Iand II of this invention contains no coloring pigment and desirably noextender pigment, and can be prepared, for example, by neutralizing thecationizable group in a base resin (a) with an acid compound such asacetic acid, formic acid, lactic acid, phosphoric acid, etc., and thenmixing and dispersing in water together with a blocked polyisocyanatecompound (b) as a crosslinking agent. The pH at the time of itselectrocoating is suitably in the range of generally 3-9, particularly5-7.

[0051] To a cationic electrodeposition paint, with a view to improvementin corrosion resistance and curability of electrocoating film, there canbe suitably blended, as circumstances might demand, organic acid salt orinorganic acid salt of a metal selected from aluminium, nickel, zinc,zirconium, molybdenum, tin, antimony, lanthanum, tungsten, bismuth,etc., in an amount of 0.1 to 10 parts by weight, particularly 0.5 to 5parts by weight, per 100 parts by weight of total solid contents of baseresin (a) and blocked polyisocyanate compound (b).

[0052] Cationic electrodeposition paint may further contain gelatinizingpolymer particles, which give rise to effects that excessive thermalfluidity can be inhibited, resulting in improved corrosion resistance(edge covering property) of edge surface portion of metal exposedportions.

[0053] Gelatinizing polymer particles are prepared by threedimensionally crosslink-polymerizing polymerizable monomers. There aresuitably usable known ones such as those which are disclosed in JapanesePatent KOKAI Publication No. Hei 2 (1990)-47173 (=U.S. Pat. No.5,021,530) and Japanese Patent KOKAI Publication No. Hei 2 (1990)-64169.Concretely, there can be mentioned gelatinizing polymer which isproduced by emulsion-polymerizing monomer (1) which has bothpolymerizable double bond and hydrolyzable alkoxysilane group, monomer(2) which has at least two polymerizable double bonds in a molecule,monomer (3) which has both polymerizable double bond and hydroxyl groupand another monomer (4) which has polymerizable double bond, in thepresence of cationically reactive emulsifier which has allyl group inits molecule.

[0054] Monomer (1) is a compound which has at least one polymerizabledouble bond and at least one hydrolyzable alkoxysilane group in amolecule. Examples of monomer (1) include vinyltrimethoxysilane,vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane,γ-methacryloxypropyltrimethoxysilane and vinyltriacetoxysilane, amongwhich γ-methacryloxypropyltrimethoxysilane is suitable.

[0055] Monomer (2) is a compound which has at least two polymerizabledouble bonds in a molecule. Examples of monomer (2) includepolymerizable unsaturated monocarboxylic acid ester of polyhydricalcohol, polymerizable unsaturated alcohol ester of polybasic acid andaromatic compound which is substituted by at least two vinyl groups.Concretely, there can be mentioned ethyleneglycol di(meth)acrylate;1,6-hexanediol di(meth)acrylate; diallylphthalate; and divinylbenzene.

[0056] Monomer (3) is a compound which has at least one polymerizabledouble bond and at least one hydroxyl group in a molecule, and whichintroduces hydroxyl group into gelatinizing polymer particles, impartshydrophilicity to said particles and functions as crosslinkingfunctional group between particles. Concretely, preferable examplesinclude 2-hydroxy(meth)acrylate and hydroxypropyl(meth)acrylate.

[0057] Monomer (4) is a compound which has polymerizable double bondother than the above-mentioned monomers (1) to (3). Examples includealkyl (having 1 to 20 carbon atoms) ester of acrylic or methacrylic acidsuch as methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate,hexyl(meth)acrylate, lauryl(meth)acrylate and cyclohexyl(meth)acrylate;vinylaromatic monomer such as styrene, α-methylstyrene and vinyltoluene;amides of acrylic or methacrylic acid; and (meth)acrylonitrile.

[0058] Constitutional proportion of these monomers is not in particularrestricted, and can be selected optionally according to objective.Preferably, however, monomer (1) is in a range of 1 to 30% by weight, inparticular 3 to 20% by weight; monomer (2) is in a range of 1 to 30% byweight, in particular 3 to 20% by weight; monomer (3) is in a range of 1to 30% by weight, in particular 3 to 20% by weight; and monomer (4) isin a range of 10 to 97% by weight, in particular 40 to 91% by weight; onthe basis of the weight of total solid contents of these monomers.

[0059] As an example of cationically reactive emulsifier which has allylgroup in its molecule, there can be mentioned a reactive emulsifierhaving quaternary ammonium salt which has the following formula:

X^(⊖)·R₁N^(⊕)(R₂)(R₃)—CH₂—CH(OH)—CH₂—O—CH₂—C(R₄)═CH₂

[0060] wherein R₁ denotes a hydrocarbon having 8 to 22 carbon atomswhich may be substituted; R₂ and R₃ each denote an alkyl group having 1to 3 carbon atoms; R₄ denotes a hydrogen atom or a methyl group; andX^(⊖) denotes a monovalent anion.

[0061] As said cationically reactive emulsifier, there can be used onewhich has already been known [from, for instance, Japanese KOKAI PatentPublication No. Sho 60 (1985)-78947], such as “Ratemuru K-180” (tradename; Kao Corporation) which has been put on the market. Such anemulsifier is used in an amount of 0.1 to 30 parts by weight, inparticular 0.5 to 5 parts by weight per 100 parts by weight of solidcontent of gelatinizing polymer particles.

[0062] The polymerization reaction of the above-mentioned monomers isconducted by emulsion polymerization which is known as a method for theproduction of acrylic polymer. Concretely, a mixture of monomers issubjected to reaction in an aqueous medium in the presence of theabove-mentioned emulsifier and a polymerization initiator such aswater-soluble azoamide compound, usually at a reaction temperature ofabout 50 to about 100° C. for about 1 to about 20 hours. Aqueousdispersion of thus obtained gelatinizing polymer particles have usuallya resin solid content of 10 to 40% by weight. Said particles have aparticle size of at most 500 nm, in particular 10 to 300 nm, and mostdesirably 50 to 100 nm. Particle size can easily be adjusted by varyingthe amount of the above-mentioned emulsifier. The amount of gelatinizingpolymer particles blended is preferably within the range of 1 to 20parts by weight, in particular 5 to 15 parts by weight, per 100 parts byweight of total solid content of base resin (a) and blockedpolyisocyanate compound (b) in the cationic electrodeposition paint.

[0063] When applied, the cationic electrodeposition paint is adjusted sothat it may have a pH of 3 to 9, preferably 5 to 7, and may have a solidcontent of at most 10% by weight, preferably 2 to 7% by weight, mostdesirably 3 to 5% by weight, and a bath temperature within a range of 25to 35° C. In the bath of said electrodeposition paint, there is dipped ashell body of a car which is produced with use of plastics-covered metalplates prepared by Processes I and II. Then, by means of currentapplication, metal exposed portions such as edge surface portions of theshell body is coated with electrodeoposition coating film. As forcurrent application condition, voltage is preferably 100 to 400 V, andcurrent application time is preferably 1 to 10 minutes. Whenelectrodeposition is conducted in this manner, an electrodepositioncoating film is formed on metal exposed portions such as edge surfaceportion which appears by the cutting of plastics-covered metal plate andthe backside or right side portion of said metal plate which is free ofplastics cover. The thickness of an electrodeposition coating film ispreferably in the range of about 5 to about 40 μm, particularly 10 to 20μm, as a cured film, on flat.

[0064] After the electrocoating is over, the article to be coated (shellbody) is drawn up from the electrobath, and, is then preferably washedwith water so that undeposited electropaint which has adhered toelectrocoated surface or electropaint which has collected in theinterior or bottom of bag-like portions may be removed.

[0065] Electrocoating film after the electrodeposition may be washedonly with a filtrate which has been prepared by ultrafiltration of apart of electropaint which had been taken from electrobath. Otherwise,said electrocoaint film may be first washed with said filtrate, and thenwith water (e.g., pure water) which is supplied to keep the liquidsurface of electrobath constant. Water which has been used for thesewater washing processes is recovered into electrobath, and, therefore,effluent is not drained outside, which manner is to be called closedsystem. Or, otherwise, electrocoating film after the electrodepositionmay be subjected to water washing in such a manner that the amount ofdrainage of wasihing water may fall within the range of at most 500 ml,preferably at most 300 ml, per square meter of electrocoated area (inwhich case, drain disposal is carried out by open system). Or again,these water washing processes may be dispensed with with.

[0066] After water washing, electrocoated film can be cured by heatingat a temperature of about 100 to about 200° C., preferably about 120 toabout 180° C., for about 10 to 40 minutes.

[0067] Through the aforementioned Processes I and II of the presentinvention, the following effects can be achieved.

[0068] (1) Since the electrodeposition paint deposits easily at theboundary portion between the plastics covering film and exposed metal,the corrosion resistance of this portion improves remarkably.

[0069] (2) Since metal plates which have previously been covered withplastics are used for the production not only of outer cover parts suchas hood panel, fender panel, door panel, luggage door panel etc. of thecar body, but also of main body consisting of underbody, side member,roof, cowl, upper back, lower back, etc., it is possible to largelyreduce the amount of the electrodeposition paint to be used at the nextstep.

[0070] (3) Since at least the outer surface of outer cover parts iscovered with a layer of plastics having a high volume specificresistance and, since, under circumstances, at least the outer surfaceof the main body is also covered with a layer of plastics having a highvolume specific resistance, the area of the portion of shell body to becoated by electrodeposition (portion with exposed metal) is small, and,consequently, the throwing power of the paint increases, andparticularly the corrosion resistance of the edge surface portion isimproved.

[0071] (4) It is possible to give the properties, which the coveringplastics have, such as chipping resistance, corrosion resistance etc.,to a car body.

[0072] (5) The use of electropaint which contains no coloring pigmentand is capable of forming a clear coating film produces the followingeffects:

[0073] 1) Thermal fluidity of coating film improves with the result thatit becomes possible to form a coating film which is excellent insmoothness and corrosion resistance even though thin. Based on thismerit, it becomes possible to shorten the current application time.

[0074] 2) Although electropaint which has permeated into joint portionsof coated article spouts out in baking process and adheres to otherportions, it causes no popping owing to good thermal fluidity, and,thus, it is possible to shorten a process of water-washing permeatedportions.

[0075] 3) Even though electrodeposition paint adheres to plastic-coveredsurfaces, there occur no uneven drying nor secondary sag marks sinceformed coating film is clear, and, thus, appearance is not damaged.

[0076] 4) In electrocoating bath, pigment or the like does not depositat horizontal portions of article to be coated, and, thus, water-washingprocess can be simplified.

[0077] (6) When there is used an electrodeposition paint which has abath solid content of at most 10% by weight, uneven drying hardly occurseven though unelectrodeposited material remains on the coated surfaceafter water washing, and, thus, decrease of appearance can be inhibited.Moreover, although electropaint which has permeated into joint portionsspouts out during baking, it hardly causes sag or popping.

[0078] (7) Owing to the use of such an electropaint, undepositedmaterial which has adhered to the elctrocoated surface needs nowater-washing for removal, or, even though it is to be water-washed,primary water washing is sufficient, with the result that water washingprocess is shortened, which is preferable in view of the preservation ofenvironment and economy.

[0079] The present invention will be described more specifically byExamples and Comparative Examples. Parts and % are by weight and thefilm thickness is that of the cured film.

[0080] 1. Preparation of Plastics-Covered Metal Plate

[0081] (a) Both sides of a polyester film with a film thickness of 16 μmwere treated by corona discharge, and, then, one side was coated with athermocurable polyester resin type adhesive to a film thickness of 7 μm,which was dried by heating at 120° C. for 30 seconds, and wound up.Next, both sides of a cold rolled steel plate of 0.8 mm thickness wereplated with alloyed molten zinc so that the plated amount may be 45g/m², and, then, were degreased and chemically treated with zincphosphate (“PB #3080 Treatment”; tradename of a product of NihonParkerrizing Co., Ltd.). One side of this metal plate was covered withthe above-mentioned polyester film by adhering with heat and pressurethrough the intermediary of adhesive, and, thus, plastics-covered metalplate was obtained.

[0082] 2. Examples and Comparative Examples

EXAMPLE 1

[0083] An (about {fraction (1/25)} scale) model of a main bodyconsisting of underbody, side member, roof, cowl, upper back and lowerback was previously prepared by cutting, molding and joining theplastics-covered metal plate (a). Furthermore (about {fraction (1/25)}scale) models of outer cover parts (car parts) such as hood, fender,door, luggage door, etc. were prepared by cutting, molding and joiningthe plastics-covered metal plate (a).

[0084] Subsequently, outer cover parts were attached to the main body toform a shell body, which was then dipped into a cationicelectrodeposition paint bath (NOTE 1), and, thus, metal exposed portionsof the shell body were electrocoated under the conditions of bathtemperature of 28° C., voltage of 200 V, and totally dipped currentpassing time of 2 minutes. Then, the shell body was inclined up and downtwice in the lengthwise direction at an angle of about 30 degrees sothat sagging electropaint might be drained off. Next, the shell body waswashed with mist spray of an filtrate which had been prepared byultrafiltration of a part of electrodeposition paint bath (NOTE 1), and,thereafter, was set for five minutes with an inclination of about 30degrees, and, then, the electrodeposition coating film was heated at170° C. for 30 minutes to be cured. The thickness of the flat portion ofthe electrodeposition coating film was 20 μm.

[0085] (NOTE 1) Cationic electrodeposition paint bath:

[0086] There were blended 70 parts (solid content) of amine addedpolyamide modified epoxy resin, 30 parts (solid content) of blockedpolyisocyanate compound (4,4-diphenylmethane diisocyanate blocked with2-ethylhexylalcohol) and 1 part of dibutyltin laurate. The resultantmixture was neutralized with 15 parts of 10% acetic acid. Then, thesolid content of this mixture was adjusted to 5% with use of deionizedwater.

EXAMPLE 2

[0087] A shell body similar to the one mentioned in Example 1 was dippedinto a cationic electrodeposition paint bath (NOTE 2), and, thus, metalexposed portions of the shell body were electrocoated under theconditions of bath temperature of 28° C., voltage of 200 V, and totallydipped current passing time of 2 minutes. Then, the shell body wasinclined up and down twice in the lengthwise direction at an angle ofabout 30 degrees so that sagging electropaint might be drained off.Next, without water washing, the electrodeposition coating film washeated at 170° C. for 30 minutes to be cured. The thickness of the flatportion of the electrodeposition coating film was 20 μm.

[0088] (NOTE 2) Cationic electrodeposition paint bath:

[0089] There were blended 70 parts (solid content) of amine addedpolyamide modified epoxy resin, 30 parts (solid content) of blockedpolyisocyanate compound (4,4-diphenylmethane diisocyanate blocked with2-ethylhexylalcohol) and 1 part of dibutyltin laurate. The resultantmixture was neutralized with 15 parts of 10% acetic acid. Then, thesolid content of this mixture was adjusted to 3% with use of deionizedwater.

EXAMPLE 3

[0090] An (about {fraction (1/25)} scale) model of a main bodyconsisting of underbody, side member, roof, cowl, upper back and lowerback was previously prepared by cutting, molding and joining a metalplate plated with alloyed molten zinc whose both surfaces wereuncovered. On the other hand, (about {fraction (1/25)} scale) models ofouter cover parts (car parts) such as hood, fender, door, luggage door,etc. were prepared by cutting, molding and joining the plastics-coveredmetal plate (a).

[0091] Subsequently, outer cover parts were attached to the main body toform a shell body, which was then dipped into a cationicelectrodeposition paint bath (NOTE 1), and, thus, metal exposed portionsof the shell body were electrocoated under the conditions of bathtemperature of 28° C., voltage of 200 V, and totally dipped currentpassing time of 2 minutes. Then, the shell body was inclined up and downtwice in the lengthwise direction at an angle of about 30 degrees sothat sagging electropaint might be drained off. Next, the shell body waswashed with mist spray of an filtrate which had been prepared byultrafiltration of a part of electrodeposition paint bath (NOTE 1), and,thereafter, was set for five minutes with an inclination of about 30degrees, and, then, the electrodeposition coating film was heated at170° C. for 30 minutes to be cured. The thickness of the flat portion ofthe electrodeposition coating film was 20 μm.

EXAMPLE 4

[0092] A shell body similar to the one mentioned in Example 1 was dippedinto a cationic electrodeposition paint bath (NOTE 3), and, thus, metalexposed portions of the shell body were electrocoated under theconditions of bath temperature of 28° C., voltage of 200 V, and totallydipped current passing time of 2 minutes. Then, the shell body wasinclined up and down twice in the lengthwise direction at an angle ofabout 30 degrees so that sagging electropaint might be drained off.Next, the shell body was washed with mist spray of an filtrate which hadbeen prepared by ultrafiltration of a part of electrodeposition paintbath (NOTE 3), and, thereafter, was set for five minutes with aninclination of about 30 degrees, and, then, the electrodepositioncoating film was heated at 170° C. for 30 minutes to be cured. Thethickness of the flat portion of the electrodeposition coating film was20 μm.

[0093] (NOTE 3) Cationic electrodeposition paint bath:

[0094] There were blended 70 parts (solid content) of amine addedpolyamide modified epoxy resin, 30 parts (solid content) of blockedpolyisocyanate compound (4,4-diphenylmethane diisocyanate blocked with2-ethylhexylalcohol), 10 parts (solid content) of gelatinizing resinfine particles and 1 part of dibutyltin laurate. The resultant mixturewas neutralized with 15 parts of 10% acetic acid. Then, the solidcontent of this mixture was adjusted to 5% with use of deionized water.

EXAMPLE 5

[0095] A shell body similar to the one mentioned in Example 1 was dippedinto a cationic electrodeposition paint bath (NOTE 3), and, thus, metalexposed portions of the shell body were electrocoated under theconditions of bath temperature of 28° C., voltage of 200 V, and totallydipped current passing time of 2 minutes. Then, the shell body wasinclined up and down twice in the lengthwise direction at an angle ofabout 30 degrees so that sagging electropaint might be drained off.Next, the shell body was washed with mist spray of an filtrate which hadbeen prepared by ultrafiltration of a part of electrodeposition paintbath (NOTE 3), and further washed with mist of pure water for theadjustment of electrobath liquid surface, and, thereafter, was set forfive minutes with an inclination of about 30 degrees, and, then, theelectrodeposition coating film was heated at 170° C. for 30 minutes tobe cured. The thickness of the flat portion of the electrodepositioncoating film was 20 μm.

Comparative Example 1

[0096] A shell body similar to the one mentioned in Example 1 was dippedinto a cationic electrodeposition paint bath which had been prepared byadjusting the solid content of the above-mentioned cationicelectrodeposition paint bath (NOTE 1) to 15%, and, thus, metal exposedportions of the shell body were electrocoated under the conditions ofbath temperature of 28° C., voltage of 200 V, and totally dipped currentpassing time of 2 minutes. Then, the shell body was inclined up and downtwice in the lengthwise direction at an angle of about 30 degrees sothat sagging electropaint might be drained off. Next, the shell body waswashed with mist spray of an filtrate which had been prepared byultrafiltration of a part of electrodeposition paint bath, and, then,the electrodeposition coating film was heated at 170° C. for 30 minutesto be cured. The thickness of the flat portion of the electrodepositioncoating film was 20 μm.

Comparative Example 2

[0097] A shell body similar to the one mentioned in Example 1 was dippedinto a cationic electrodeposition paint bath (“Elecron #9600”, tradenameof a product of Kansai Paint Co., Ltd; Gray color) having a solidcontent of 20%, and, thus, metal exposed portions of the shell body wereelectrocoated under the conditions of bath temperature of 28° C.,voltage of 200 V, and totally dipped current passing time of 2 minutes.Then, the shell body was inclined up and down twice in the lengthwisedirection at an angle of about 30 degrees so that sagging electropaintmight be drained off. Next, the shell body was washed with mist spray ofan filtrate which had been prepared by ultrafiltration of a part ofelectrodeposition paint bath (“Elecron #9600”), and, then, theelectrodeposition coating film was heated at 170° C. for 30 minutes tobe cured. The thickness of the flat portion of the electrodepositioncoating film was 20 μm.

[0098] 3. Performance Test Results

[0099] The electrocoating films which were formed in Examples andComparative Examples were visually observed with respect to stains ofuneven drying, marks of secondary sagging and of popping caused byelectropaint which had spouted out from joints, and edge corrosionresistance. The results are shown in Table 1. TABLE 1 ComparativeExamples Examples 1 2 3 4 5 1 2 Uneven drying ◯ ◯ ◯ ◯ ◯ Δ X Marks ofsecondary sagging Δ Δ Δ Δ ◯ X X and of popping Edge corrosion resistance◯ ◯ ◯ ⊚ ⊚ ◯ ⊚

[0100] Test Methods:

[0101] Uneven drying:

[0102] ◯ shows that there was observed no stain of uneven drying ofadhered electropaint liquid; Δ shows that stains of uneven drying ofadhered electropaint liquid was seen a bit; and X shows that stains ofuneven drying of adhered electropaint liquid were seen remarkably allover.

[0103] Marks of secondary sagging and of popping:

[0104] ◯ shows that there was observed no marks of sagging and ofpopping caused by electropaint which had spouted out from joints, andthat the appearance was good; Δ shows that marks of sagging (unevenness)and of popping were seen a bit, and that the appearance was no good; andX shows that marks of sagging (unevenness) and of popping were seenremarkably, and that the appearance was no good.

[0105] Edge corrosion resistance:

[0106] The models which had been electrocoated in Examples andComparative Examples were placed in a salt spray resistance test machine(35° C.), and, after 240 hours, the corrosion resistance at the acuteangle edge of cut portion of plastics-covered steel plate of the shellbody was observed.

[0107] ⊚ shows that no rust was observed at edge surface portion; ◯shows that the occurrence of rust was slightly seen at the edge surfaceportion; is observed at all, Δ shows that the occurrence of rust andblisters was observed a bit at the edge surface portion; and X showsthat the occurrence of rust and blisters was remarkably seen at the edgesurface portion.

1. A car body coating process which is characterized in that the main exterior of a car body is produced with use of plastics-covered metal plates to form a shell body, and that the metal-exposed portion of the shell body is electrocoated with an electrodeposition paint which contains no coloring pigment and has a bath solid content of at most 10% by weight and which is capable of forming a clear coating film.
 2. A car body coating process which is characterized in that car parts which are made by cutting, molding and joining plastics-covered metal plates are attached to the main exterior of main body which has previously been assembled, and that thus formed shell body has its metal-exposed portions electrocoated with an electrodeposition paint which contains no coloring pigment and has a bath solid content of at most 10% by weight and which is capable of forming a clear coating film.
 3. A process of claim 1 or claim 2 wherein the plastics-covered metal plate is prepared by sticking a film-like or sheet-like plastic onto a metal plate.
 4. A process of claim 3 wherein the film-like or sheet-like plastic is stuck onto a metal plate via an adhesive
 5. A process of claim 1 or claim 2 wherein the thickness of plastic layer on the plastics-covered metal plate is in the range of 3 to 75 μm.
 6. A process of claim 1 or claim 2 wherein the electrodeposition paint does not substantially contains extender pigment either.
 7. A process of claim 1 or claim 2 wherein the electrodeposition paint has a bath solid content of 2 to 7% by weight.
 8. A process of claim 1 or claim 2 wherein the electrodeposition paint has a bath solid content of 3 to 5% by weight.
 9. A process of claim 1 or claim 2 wherein the electrodeposition paint is of cationic type.
 10. A process of claim 9 wherein the electrodeposition paint comprises a base resin (a) having hydroxyl group(s) and cationizable group(s) and a blocked polyisocyanate compound (b) as a crosslinking agent, and, as circumstances might demand, gelatinizing polymer particles as well.
 11. A process of claim 10 wherein the base resin (a) is a resin which is obtained by further making a cationizing agent react with epoxy resin which has been prepared by reaction between polyphenol compound and epichlorohydrin.
 12. A process of claim 10 wherein the proportion of base resin (a) is within a range of 40 to 90% on the basis of the weight of total solid contents of base resin (a) and blocked polyisocyanate compound (b).
 13. A process of claim 10 wherein the proportion of gelatinizing polymer particles is within a range of 1 to 20 parts by weight per 100 parts by weight of total solid contents of base resin (a) and blocked polyisocyanate compound (b).
 14. A process of claim 1 or claim 2 wherein the coating film which is formed by electrodeposition coating has a thickness in the range of 5 to 40 μm.
 15. A process of claim 1 or claim 2 wherein electrocoating film after the electrodeposition is subjected to water washing in such a manner that the amount of drainage of washing water is at most 500 ml per square meter of electrocoated area.
 16. A process of claim 15 wherein coating film after the electrodeposition is washed either with ultrafiltration filtrate alone or firstly with ultrafiltration filtrate and subsequently with pure water for the adjustment of electrobath liquid surface.
 17. A process of claim 1 or claim 2 wherein the step of water washing of coating film after the electrodeposition is omitted.
 18. A process of claim 1 or claim 2 wherein coating film after the electrodeposition is cured by heating at a temperature of about 100° C. to about 200° C.
 19. A car body which is coated by the process of claim 1 or claim
 2. 